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Polymers: Permeation Damage of Polymer Liner in Oil and Gas Pipelines: A Review
Polymers: Permeation Damage of Polymer Liner in Oil and Gas Pipelines: A Review
Review
Permeation Damage of Polymer Liner in Oil and Gas
Pipelines: A Review
Hafiz Usman Khalid *, Mokhtar Che Ismail and Norlin Nosbi
Department of Mechanical Engineering, Universiti Teknologi PETRONAS, Perak 32610, Malaysia;
mokhtis@utp.edu.my (M.C.I.); norlin.nosbi@utp.edu.my (N.N.)
* Correspondence: hafiz_19001708@utp.edu.my
Received: 21 August 2020; Accepted: 11 September 2020; Published: 09 October 2020
Abstract: Non-metallic pipe (NMP) materials are used as an internal lining and standalone pipes in the
oil and gas industry, constituting an emerging corrosion strategy. The NMP materials are inherently
susceptible to gradual damage due to creep, fatigue, permeation, processing defects, and installation
blunder. In the presence of acid gases (CO2 , H2 S), and hydrocarbons under high pressure and
temperature, the main damage is due to permeation. The monitoring of possible damage due to
permeation is not well defined, which leads to uncertainty in asset integrity management. Assessment
of permeation damage is currently performed through mechanical, thermal, chemical, and structural
properties, including Tensile Test, Differential Scanning Calorimetry (DSC), Fourier-transform Infrared
Spectroscopy (FTIR), and Scanning Electron Microscopy (SEM)/Transmission Electron Microscopy
(TEM), to evaluate the change in tensile strength, elongation, weight loss or gain, crystallinity, chemical
properties, and molecular structure. Coupons are commonly used to analyze the degradation of
polymers. They are point sensors and did not give real-time information. Their weight and mechanical
properties are used to analyze them. Polymers are dielectric materials, and this dielectric property
can be studied using Impedance Analyzer and Dielectric Spectroscopy. This review presents a
brief status report on the failure of polymer liners in pipelines due to the exposure of acid gases,
hydrocarbons, and other contaminants. Permeation, liner failures, the importance of monitoring,
and new exclusive (dielectric) property are briefly discussed. An inclusive perspective is provided,
showing the challenges associated with the monitoring of the polymer liner material in the pipeline
as it relates to the life-time prediction requirement.
1. Introduction
Pipelines play a substantial and dynamic role in the transportation of crude oil and natural
gas. Crude oil and natural gas contain various corrosive contaminants such as CO2, H2 S, water,
and microbes. CO2 corrosion (sweet corrosion) and H2 S corrosion (sour corrosion) are the most
prevalent forms of corrosion [1,2]. The rate of internal corrosion in wells and pipelines is influenced by
CO2 and H2 S content, water, flow velocity, and surface condition of the material.
Internal pipeline corrosion can be mitigated by several means, including the selection of appropriate
material, use of corrosion inhibitors, metallic and non-metallic linings, or coatings [3]. The practice of
using non-metallic pipe (NMP) materials in oil and gas production and transportation is emerging
as a viable and reliable solution to mitigate corrosion. Polymers and composites both fall under
the category of NMP, but we only discuss polymers in this article and specifically thermoplastics.
NMP materials have applications in both onshore and offshore pipelines [4]. NMP has the advantage
of low weight and better corrosion resistance as compared to metals. However, the possibility of
permeation under high temperature-pressure, hydrocarbons, and acidic gases limits the application [5].
Thus, the systematic evaluation of possible degradation mechanisms and phases is critical for the
successful use of NMP materials.
Permeation is a slow process and requires sensitive monitoring methods. Currently, test coupons
are used for monitoring NMP degradation. These coupons were inserted in the pipelines, and after
some specific time intervals, they are retrieved and evaluated based on using molecular weight as
a measuring indicator. The coupons method only provides qualitative measuring for degradation
mechanism, but no real time information is possible, therefore it needs to be further explored in terms
of quantitative measures.
corrosion inhibitors depends on the fluid composition, quantity of water, and flow regime [16,21,22].
Table 1 sheds some light on the corrosion mitigation strategies in the oil and gas environment [9].
(a) Organic and Inorganic (1) They are used for internal and
Coatings
(b) Metallic external protection.
The emerging alternative is NMP for combating internal pipeline corrosion. These liners are
preferred as the most feasible corrosion management solution in cases where the long-term reliability
of chemical corrosion inhibition systems is not suitable, and sometimes the inhibitor consumption rate
is so high that it becomes more expensive than a liner over the lifetime of the pipeline. NMP materials
are considered to be one of the best available and most feasible measures to prevent pipeline integrity.
Multi-layer foil composite (MLFC) performs better for corrosion protection as compared to most
thermoplastics including LDPE, HDPE, and nylon. Corrosion protection of steel pipelines with
metal-polymer composite barrier liners [27]. The pipelines equipment’s of the ships are made from
Polymer composite material (PCM) with several properties including higher strength to mass ratio,
chemical inertness, low thermal conductivity, and better protection against electrochemical corrosion.
Three-layer PCM pipelines provide the most enhanced shield against the flowing gases (CO, CO2 ) in
the pipelines at higher temperatures. The inner shell provides rigidity and reduces the environmental
temperature effect that improves the pipeline’s life [28].
Thermoplastics liners follow the NACE RP-0304 standard 2nd edition for their design, installation,
and operation in the oilfield pipelines. ISO 23936-1:2009 provides a summary regarding the performance
of different thermoplastics with interaction with produced water, oil, and gas media along with
chemical treatment [29]. Table 2 shows the usage of different NMP materials in the oil and gas pipeline
applications. Figure 1 shows the different layers present inside the glass reinforced plastic (GRP) pipe
while Figure 2 shows the internal and outer structure RTP pipe.
Material Properties
1. Due to the presence of C-F bonds, it has a high melting point (177 ◦ C) and excellent
mechanical properties, which gives powerful resistance to the fluids producing in the oil
and gas environments.
2. With exceptional features, including good abrasion and chemical resistance, low
coefficient of friction, and low moisture absorption [41].
3. Its mechanical and thermal stability with a working temperature limit of 130 ◦ C makes it
suitable for liner applications [42].
PVDF 4. Recommended using in the presence of petroleum products, O2 , CO2, and chlorinated
water within the temperature range of 110–125 ◦ C.
5. It is not affected in the presence of alcohol, chlorinated solvents, aromatic and aliphatic
hydrocarbons [43].
6. PVDF-PLP can be used in acidic service conditions for oil and gas flowlines, it is
cost-effective than CRA and has better flow assurance properties [42].
7. PTFE and Perfluoroalkoxy alkane (PFA) can handle a variety of solvents, including acids,
alkalis, and corrosive fluids up to a working temperature range of 160 ◦ C [44].
Polymers 2020, 12, 2307 5 of 31
Table 2. Cont.
Material Properties
1. GRE (Glass Reinforced Epoxy) has a high strength to weight ratio, easy installation,
GRE and a better life span [45].
Polymers 2020, 12, x 2.
FOR PEER
TheyREVIEW 4 of 32
are used for extensively employed for transporting corrosive hydrocarbons [46,47].
Polymers 2020, 12, x FOR PEER REVIEW 4 of 32
Figure
Figure 1.
1. GRP
GRP Pipe
Pipe [30].
[30].
Figure 1.
Figure
Figure 2.
2. RTP
RTP structural
structural components
components adapted
adapted from
from [31].
[31].
Figure 2. RTP structural components adapted from [31].
Figure
Figure 3.
3. Flexible
Flexible pipe
pipe [64].
[64].
As we see from Figure 4, there are many failures adopted by NMP. NMP. Still,
Still, permeation
permeation is the
prominent one, andand ititwas
wasstudied
studiedby byvarious
variousresearchers
researchersupup until
until now
now in different
in different environments
environments on
on different
different materials.
materials. Permeation
Permeation being
being thethe dominating
dominating factorininthe
factor thepolymer
polymer liner
liner failure. In
In the
presence
presence ofofhydrocarbons,
hydrocarbons, polyolefins swellswell
polyolefins as they
as both
theyhave
botha similar
have achemical
similar structure.
chemical Polyamide
structure.
degrades
Polyamide due to the presence
degrades of presence
due to the water at higher temperatures
of water [66].
at higher temperatures [66].
2.2.1. Permeation
2.2.1. Permeation
Permeation
Permeation is is aa molecular
molecularphenomenon,
phenomenon,involving
involvingthethepassage
passageofofa afluid,
fluid,gas,
gas,ororvapor
vaporthrough
througha
material.
a material.ItItisisa anaturally
naturallyoccurring
occurringphenomenon,
phenomenon,so soititisisaavery
verymuch
much vitalvital process
process toto focus
focus on
on the
the
subject matter. Permeation is a function of two variables:
subject matter. Permeation is a function of two variables:
1.
1. Diffusion (D) between molecular chains
Diffusion
2. Solubility (s)
Solubility (s) of
of the
the permeant
permeant in the polymer
a route into the polymer bulk. Fick’s law of diffusion best describes permeation models. It provides
the following Equation.
Q = Ds (1)
where Q(Pe) is permeation coefficient, D is the diffusion coefficient, and s is the solubility coefficient.
Thermal expansion and hydrocarbon swelling will generate stresses in the liner material,
which leads to buckling or collapse of the liner. Thermoplastics give a free path for gases, vapors,
Polymers 2020, 12, x FOR PEER REVIEW 8 of 32
and water to pass through them. Barrer was the first one to explain that the diffusion of molecules
through rubbery polymer is a thermally initiated process [71]. Permeation mainly depends on the
is a thermally initiated process [71]. Permeation mainly depends on the number of critical factors,
number of critical factors, including liner thickness, partial pressure, % crystallinity, crosslinking, size
including liner thickness, partial pressure, % crystallinity, crosslinking, size of the permeant, and the gap
of the permeant, and the gap between the liner and the host steel pipe [72]. The presence of a higher
between the liner and the host steel pipe [72]. The presence of a higher degree of crystallinity lowers the
degree of crystallinity lowers the diffusion and solubility in PE [73]. The process of permeation is
diffusion and solubility in PE [73]. The process of permeation is primarily a function of temperature.
primarily a function of temperature. Temperature affects gas permeation prominently [74,75]. Diffusion
Temperature affects gas permeation prominently [74,75]. Diffusion and permeation parameters are
and permeation parameters are temperature-dependent. They increased by increasing the temperature
temperature-dependent. They increased by increasing the temperature while solubility had an opposite
while solubility had an opposite relation with it. Henry gave the law of absorption, which explained
relation with it. Henry gave the law of absorption, which explained the direct relationship between
the direct relationship between solubility and pressure. It is not always linear, which was stated by
solubility and pressure. It is not always linear, which was stated by Langmuir, BET, and dual sorption
Langmuir, BET, and dual sorption models that the permeation coefficient may or may not vary with
models that the permeation coefficient may or may not vary with pressure [76].
pressure [76].
Permeation through NMP materials is a distinct aspect of the degradation of pipelines. It happens
Permeation through NMP materials is a distinct aspect of the degradation of pipelines. It happens
due to the exposure of acidic gases and immersion in hydrocarbons, including acids in the presence of
due to the exposure of acidic gases and immersion in hydrocarbons, including acids in the presence of
temperature and pressure. Table A2 sheds some light on the permeation and absorption of gases and
temperature and pressure. Table A2 sheds some light on the permeation and absorption of gases and
liquids present in the oil and gas pipelines through different types of NMP materials.
liquids present in the oil and gas pipelines through different types of NMP materials.
We can conclude from Table A2 that how different gases present in the environment of the
We can conclude from Table A2 that how different gases present in the environment of the pipeline
pipeline affect the liner materials. Figure 5 shows the study of various gases in permeation from 1996–
affect the liner materials. Figure 5 shows the study of various gases in permeation from 1996–2020.
2020.
Figure 5.
Figure 5. Different
Different types
types of
of gases
gases and
and fluids
fluids used
used in
in permeation
permeation experiments.
experiments.
Temperatureand
Temperature andpressure
pressurealso
alsoplay
playan
animportant
importantrole
rolein
inthe
thepermeation
permeationphenomenon.
phenomenon. The
The different
different
polymeric material
polymeric material behavior was assessed
assessed using these
these parameters.
parameters. Figure shows the
Figure 6 shows the percentage
percentage of
of
research articles
research articles published
publishedononthese
theseparameters
parameterswithin thethe
within previous years
previous from
years 1996–2020.
from 1996–2020.
Polymers 2020, 12, 2307 9 of 31
Polymers 2020, 12, x FOR PEER REVIEW 9 of 32
Figure
Figure 6.
6. Process
Process Parameters
Parameters in
in Permeation
Permeation Experiment.
Experiment.
2.2.2.
2.2.2. Flexible
Flexible Pipelines
Pipelines
Permeation
Permeation is isaavital
vitalparameter
parametertoto consider
consider during
during thethe lifetime
lifetime of flexible
of flexible pipes.
pipes. The vents
The vents are
are most
most commonly present on the connection end fittings. It follows two problems,
commonly present on the connection end fittings. It follows two problems, one that the permeate gases one that the
permeate
most likelygases most likely
to corrode to corrode the reinforcements.
the reinforcements. The other one isThe thatother one iscondenses
the water that the water condenses
in the annulus
in
andthe annulus
restrict theand
flowrestrict the Due
of gases. flowtoofthis
gases. Due to this phenomenon,
phenomenon, the buildup ofthe buildup
pressure of pressure
occurs, which occurs,
in turn
which in turn causes the outer sheath to burst. Some state-of-the-art solutions were
causes the outer sheath to burst. Some state-of-the-art solutions were given in U.S Patent. The removal given in U.S
Patent. The removal
of permeate gases was ofcarried
permeateout gases was carried
by injecting out(N),
inert gas by injecting inertthem
which forces gas (N), which
along forces them
the venting path;
along the venting path; another one is to use a suction pump [77]. PVDF is
another one is to use a suction pump [77]. PVDF is susceptible to water permeation. It was proved susceptible to water
permeation. It was proved by a large-scale test at 100 °C and 50 bar in the presence of CH4 and CO2
gases. The permeation of CO2 is more than CH4 [78]. IFP and Technip provided a solution to obstruct
Polymers 2020, 12, 2307 10 of 31
by a large-scale testPEER
at 100 ◦ C and 50 bar in the presence of CH4 and CO2 gases. The permeation
Polymers 2020, 12, x FOR REVIEW 10 of 32
of CO2 is more than CH4 [78]. IFP and Technip provided a solution to obstruct H2 S permeation.
H 2S permeation.
Anti-H Anti-H2S PEZnO
2 S layer containing layer containing
was placedPEZnO between was theplaced
pressure between
sheaththe andpressure
annulus sheath and
to its effect.
annulus
The reactionto itsbetween
effect. The oxidereaction between
and this anti-Hoxide and this
2 S layer gaveanti-H 2S layer
a purple color,gave a purple
which color, which
was observed by
was observed
the optical by the optical
microscopy and EPMAmicroscopy
[79]. Due and to EPMA
a higher[79].percentage
Due to a higherof ethanolpercentage
content of ethanol
(85%) and
content (85%) swelling
temperature, and temperature,
occurred,swelling
which inoccurred,
turn increasedwhich in theturn
fluxincreased
across thethe fluxmulti-layer
PA12 across the PA12 pipe.
multi-layer
The delamination pipe. The delamination
of the inner PA12oflayerthe inner
fromPA12 PVDF layer
duefrom
to the PVDF due to
presence ofthe presence
ethanol fuel.ofThe
ethanol
loss
fuel. The loss of plasticizer at higher temperatures affects the performance
of plasticizer at higher temperatures affects the performance of the pipeline [80]. Hydrolysis is the of the pipeline [80].
Hydrolysis
central primary is the central
damage forprimary damage
PA in flexible pipesforinclude
PA in the flexible pipes
breaking of include the breaking
amide linkages of amide
in the backbone,
linkages
reducinginthe themolecular
backbone,weight.
reducingThree
the molecular
dog boneweight. specimens Three dogtaken
were bone specimens
from threewere takenlayers
different from
three different layers of the flexible
◦ pipe operated at 80 °C for three
of the flexible pipe operated at 80 C for three years. The aging of PA is monitored by the solution years. The aging of PA is
monitored by the solution
viscosity (CIV-corrected viscosity
inherent (CIV-corrected
viscosity) value, and inherent viscosity)
it decreased due value, andscission.
to chain it decreased due to
Plasticizer
chain scission. due
loss happened Plasticizer
to high loss happened
temperature due toThe
service. high temperature
elastic modulus service.
decreases Thewith elastic modulus
an increase in
decreases with an increase in CIV value. The degree of crystallinity increased
CIV value. The degree of crystallinity increased due to the phenomenon of chemi-crystallization [81]. due to the phenomenon
of
Thechemi-crystallization
durability of the aliphatic [81]. The durability
polyamides of the
with long aliphatic polyamides
alkyl chains such as withPA11longand PA12alkyl chains such
gave higher
as PA11 and PA12 gave higher strength in the severe environment to
strength in the severe environment to inner sheath failure. The plasticizer loss is also a critical factorinner sheath failure. The
plasticizer
in materialsloss is also a critical
embrittlement. factor and
Fracture in materials
tensile testsembrittlement.
were carriedFracture and tensile
out at different tests were
temperatures,
carried
and CIVout at different
values temperatures,
were measured. and CIV
No necking valuesduring
appears were measured.
the tensile No test,necking
and theappearsdeformation during is
the tensile test, and the deformation is homogenous. PA showed a
homogenous. PA showed a brittle behavior at lower values of CIV and vice versa [55]. HDPE is abrittle behavior at lower values of
CIV and vice material,
hydrophobic versa [55]. butHDPE is a hydrophobic
susceptible to aromaticmaterial,
hydrocarbons but susceptible
and cyclicto aromatic
solvents. It hydrocarbons
is appropriate
and cyclic solvents. It is appropriate for use in hydrocarbons ◦ within
for use in hydrocarbons within the temperature range of 45 C to 60 C. However, in the presence the
◦ temperature range of 45 °C of
to 60 °C. However, in the presence of hydrocarbons,
hydrocarbons, they tend to swell and lose their strength [5,82]. they tend to swell and lose their strength [5,82].
Now
Now we we know
know thatthat different
differentpolymers
polymersare aredegraded
degradedinindifferent
differentspecific
specificenvironments.
environments.Figure Figure8
8shows
showsthethe temperature
temperature limits for using these polymer materials in the oil and
limits for using these polymer materials in the oil and gas industry in gas industry in diverse
environments.
diverse environments.
Figure 8.
Figure Temperature limits for Polymers.
8. Temperature
pressure change. Cross-linked polyethylene (XLPE) and PVDF are the most influential polymers
for high-pressure CO2 applications [83]. The contact triggered the swelling and plasticization of the
polymer, which in turn reduced the mechanical properties and increased the permeation rate. There is
a chance of blistering in terms of decompression.
In Deepwater offshore, the pipelines face a more chemically aggressive environment, including
supercritical CO2 (scCO2 ). Unfortunately, they degrade with time. Experiments were run to predict
the life of PA12 in the presence of crude oil with water and scCO2 . The respected material did not
perform well in the scCO2 environment and degrade earlier as compared to other environments [84].
The permeation was carried out at 45, 60, 75, 90 ◦ C and 100 bars. The solubility increases with increment
in pressure but decreases with higher temperatures for both polymers. Due to proximity to the critical
point, the behavior of solubility was quite unusual at 100 bars [83].
PVDF was used due to its high temperature bearing capacity in the offshore risers. The effect of
scCO2 on PVDF was evaluated. The high-pressure CO2 has a synergetic effect on the material and
equipment. The increase in volume (24.17%) occur, followed by a decrease in density (12.5%), and the
sample color changed. The reduction in mechanical properties was observed, including decrement in
hardness and elastic modulus. The fracture surface showed the ductile behavior of the sample due to
the softening of gas [85].
For downhole applications, the pressure keeps on rising, and the material needs to have higher
mechanical strength and corrosive resistance. The performance of HDPE, XLPE, and PA11 was
evaluated in the presence of supercritical CO2 fluid. The operating temperature and pressure were
95 ◦ C and 241 bars. The properties, including yield strength, decreased, and % elongation increased for
HDPE and PA, but no change observed for XLPE [86]. PVDF and MDPE were tested for permeation in
scCO2 at 77 ◦ C and within a pressure range from 1–1000 bars. Well, other cases reported the coefficient
of thermal expansion was reduced in the presence of supercritical fluid (CO2 ). As soon as the pressure
increases, the sorption kinetics improved, and the fluids penetrate through the interstitial sites of the
amorphous phase, degraded the mechanical properties [87].
The permeation experiment was carried out with MDPE and PVDF at 118 ◦ C and 430 bars in the
presence of scCO2 . The swelling did not affect solubility around 100 bars, but above it, the change
in volume was significant. The derived equation showed the key importance of gas density with its
solubility as well as the geometry of the sample did not affect the solubility as long as the system is in
equilibrium [88]. NKT flexibles have carried out an extensive qualification program for polymer liners
in high-pressure CO2 applications. XLPE liner passed the blistering and high decompression test in
the presence of 90 ◦ C/650 bars CO2 due to its crosslinking effect in structure [89].
Characterization
Research Article Materials Parameters Time Interval
Techniques
CO2 , H2 S, O2 and TH 4XX
Fu, et al. [90] HDPE formation water, 80, 110 and 562 days & 30 days Tensile test
140 ◦ C 10MPa
ClO2 Immersion, 60 ◦ C SEM, Tensile test,
Bredács, et al. [91] PE (2 grades) 1 ppm One Week FTIR, Dynamic
5 & 10 ppm Oxidation Test
Hot Air &
PE-RT De-ionized water
Grabmann, et al. [92] 77 to 1372 days Tensile Test, DSC
PP-R 115 ◦ C, 50 ◦ C, 95 ◦ C &
135 ◦ C, 115 ◦ C, 95 ◦ C
Crude Oil Instrument
de Oliveira, et al. [93] PVDF 80 ◦ C 30, 120, 320 days Indentation
1 atm Technique
Diesel Thermogravimetric
Torres, et al. [94] HDPE 150 days
20 ◦ C & 50 ◦ C & FTIR
Deionized water,
Romão, et al. [57] PA11 (plasticized) Oilfield water 30 & 50 days DSC, SEM, XRD
110, 120 & 140 ◦ C
Ghabeche, et al. [95] HDPE Toluene-methanol Ambient 7 & 1290 days DSC, tensile test
Cracking appears in the HDPE specimen when the temperature exceeds 80 ◦ C, and the %
elongation is reduced following the increase in temperature [90]. The thickness comparison was carried
out as the minimum thickness polymer showed faster aging and embrittlement due to the formation of
surface cracks. The simultaneous reduction of elongation at break and oxidative onset temperature
(OOT) indicate the reaction of ClO2 with AO (antioxidants) and polymer molecules. Various peaks
were observed in the FTIR curve, indicating phenolic AO degradation [91]. After induced aging in hot
air and deionized water, PE-RT and PP-R showed higher enthalpy values. Due to the temperature
increase, the strain at break decreases [92]. PVDF presents low hardness and elastic modulus values,
in the presence of crude oil. Plasticization occurs due to the swelling of polymer material [93].
The embrittlement of both PE grade materials was demonstrated by an increase in the carbonyl
index value. Degradation of mechanical properties is attributed to the reduction of molar weight
caused by the β-scission of alkoxy radicals [96]. Diffusion and degradation of low molecular weight
chains occur in HDPE due to aging in the presence of diesel lubricants. No chemical modification in
the structure was observed [94]. Mechanical properties and the crystalline structure were unaffected
after one year of exposure to hydrogen gas [97]. Oligomers were formed by the hydrolysis of PA11
in the polymer matrix. The degree of crystallinity rises with respect to aging. CIV values tend to be
lower at higher temperatures. Due to immersion in the oilfield water (pH = 5.5) for 50 days, surface
cracks emerge in the SEM images [57]. Structural properties and shore hardness were measured after
exposure of TM mixture to PE. The surface roughness of the internal surface increased after 1290 days.
Structural changes occurred due to aging in the presence of TM mixture and properties, including % age
crystallinity and thermal stability of material decreased. The value of Young’s modulus significantly
dropped, and the pipe shifted toward brittle behavior [95].
3.1. Coupons
Coupons are used because of their simple working principle and smooth operation. However,
installation, removal, and lab analysis require an extended period. Inline monitoring using mounted
test coupons is one of the techniques to test polymer aging. It does not represent the most critical
bore environment, so it is not that feasible. Installing coupons on remote, buried pipelines is often
impractical at susceptible locations. They are point sensors with limited sensing coverage and did
not provide real-time information on oil and gas infrastructures. Force Technology, one of the leading
Polymers 2020, 12, 2307 13 of 31
companies, implicates the monitoring of flexible risers using vent gas monitoring, polymer coupon
monitoring, and load and response monitoring. Coupons are used to monitor the integrity of the
polymer sheath layer within the flexible risers. They are placed in the pipeline to be exposed to the
same conditions. Coupons are retrieved for monitoring and examined with their patented method for
evaluating the integrity of the polymer sheath [98]. The dielectric sensing technique for the degradation
Polymers
of 2020, 12,
polymer usesx FOR
testPEER REVIEW
coupons placed inside the pipe bore rather than test coupon removal, but 13 of
it 32
is
under development now [99].
Pressure sheaths
Pressure sheaths of of the
the production
production flexible
flexible pipes
pipes on on the
the Atlanta
Atlanta field
field are
are made
made of ofPA12
PA12 material.
material.
To ensure the mechanical integrity of the pipeline, polymer coupons
To ensure the mechanical integrity of the pipeline, polymer coupons were installed for monitoring were installed for monitoring the
the condition
condition of the
of the pressure
pressure sheath.
sheath. TheThe coupons
coupons were
were removed
removed regularly,
regularly, and andthethe molecular
molecular weight
weight is
is their measuring indicator. The analysis to assess deterioration will
their measuring indicator. The analysis to assess deterioration will follow the methodology outlined in follow the methodology
outlined
the in the [100].
API 17TR2 API 17TR2It was[100]. It was briefed
previously previously briefed
in one of theinU.S.
onePatents
of the U.S. Patents
to predict toand
life predict life and
monitor the
changes in the installed coupons. Coupons were tested in the lab by accelerating the parametersthe
monitor the changes in the installed coupons. Coupons were tested in the lab by accelerating to
parameters to achieve physical and chemical aging. However, before running
achieve physical and chemical aging. However, before running the experiment, these pre-aged coupons the experiment, these
pre-aged
were coupons
evaluated for were
differentevaluated for different
properties, includingproperties, including
tensile strength, tensile elasticity,
modulus, strength, and modulus,
crack
elasticity, and crack initiation and propagation [101]. Before the testing
initiation and propagation [101]. Before the testing of grooved liners in the pipelines, coupons were of grooved liners in the
pipelines, coupons were placed to verify the performance of the material
placed to verify the performance of the material [86]. One of the fields in Canada had a project of [86]. One of the fields in
Canada had a project of installing PA12 liner. Before the installation, coupons
installing PA12 liner. Before the installation, coupons were installed for one year. Mechanical properties were installed for one
year.molecular
and Mechanical properties
weight and molecular
were determined afterweight were determined
the retrieval after the retrieval
[102]. For predicting the life of[102].
pressure For
predicting the life of pressure sheath in a flexible pipe, the aging of Rilsan
sheath in a flexible pipe, the aging of Rilsan (PA11) was monitored by placing the coupons inside the (PA11) was monitored by
placing the coupons inside the flowline. Coupons are served as an integrity
flowline. Coupons are served as an integrity management tool [103]. Due to degradation mechanisms management tool [103].
Due to
such degradation
as hydrolysis andmechanisms such as chain
oxidation, polymer hydrolysis
scission and oxidation,
occurs, which polymer
gives shorter chain scissionofoccurs,
segments chain.
which gives shorter segments of chain. It will affect the elongation
It will affect the elongation at break value suddenly. One novel method was developed at break value suddenly.
to measureOne
novel
the massmethod
fractionwasofdeveloped
polymer. PA11 to measure
material thewas
mass fraction into
separated of polymer.
individual PA11 material
chains. These was separated
chains were
into individual chains. These chains were separated by size and the
separated by size and the size is measured by refractive index or UV absorption technique. Then size is measured by refractive
these
index or UV
molecular absorption
weights can betechnique.
analyzed by Then
thethese molecular
computer [104]. weights
Figure 9a,b canshows
be analyzed
the disk byshape
the computer
polymer
[104]. Figure 9a,b shows the disk
coupon and its insertion in the pipeline. shape polymer coupon and its insertion in the pipeline.
(a) (b)
Figure 9. (a)
(a) Polymer
Polymer coupon
coupon in the pipeline, (b) coupon and holder.
3.2. Dielectrics
3.2. Dielectrics
A
A dielectric
dielectric material
material is
is aa substance
substance that
that is
is aa poor
poor conductor
conductor of of electricity
electricity or
or an
an insulator
insulator but
but can
can
be polarized by the electrostatic field. Polymers are dielectric materials, and they can be electrically
be polarized by the electrostatic field. Polymers are dielectric materials, and they can be electrically
polarized
polarized by
by applying
applying anan external
external field.
field. Polar
Polar and
and non-polar
non-polar groups
groups characterize
characterize them.
them. Dielectric
Dielectric
materials
materials are
are solids,
solids, including
including ceramic,
ceramic, glass,
glass, and
and plastics. The extent
plastics. The extent to
to which
which the
the material
material can
can
concentrate the electrostatic lines of flux is dielectric constant. If the voltage is high, the field becomes
concentrate the electrostatic lines of flux is dielectric constant. If the voltage is high, the field becomes
too intense, and the material is damaged permanently. Important parameters describing polymers
dielectric behavior are dielectric constant and dissipation factor. Dielectrics provide impedance to the
flowing AC current, impedance includes both the resistive and the reactance components [105].
Different techniques are present to find dielectric properties, including Impedance Analyzer and
Dielectric Spectroscopy.
Polymers 2020, 12, 2307 14 of 31
too intense, and the material is damaged permanently. Important parameters describing polymers
dielectric behavior are dielectric constant and dissipation factor. Dielectrics provide impedance to
the flowing AC current, impedance includes both the resistive and the reactance components [105].
Different techniques are present to find dielectric properties, including Impedance Analyzer and
Dielectric Spectroscopy.
Dielectric spectroscopy is used to measure the permittivity or dielectric constant of the polymeric
materials as a function of frequency [106,107]. It can also be done by as a function of time or temperature
at fixed frequencies to determine the physical and chemical properties of polymer. It also gives
fundamental understanding of the molecular dynamics processes in polymers. Dipole reorientation
(permanent and induced) and conduction of ions or electrons in the present of electric field contribute
to the dielectric response of the material.
The permeation fluxes can be found using the Flory–Huggins and Maxwell–Stefan models.
Both models describe the thermodynamics and equilibrium of the polymer solution [70]. These models
are gaining popularity with time. It is one of the methods used to find the permeation across
polymeric materials.
4. Conclusions
Carbon Steel pipelines are prone to corrosion attacks. NMP plays a promising role as a liner to
prevent the pipelines from deteriorating due to their proficient features such as their light weight,
low cost, ease of installation, chemically, and thermal inertness. Polymer pipes do not have a prolonged
life due to permeation damage. They have an inherent nature to provide pathways to hydrocarbons
and gases to permeate through them. Plasticization and swelling occurred as a result of hydrocarbon
absorption. Certain important characteristics, such as tensile strength and elastic modulus decline.
Many other scholars explored the permeation of acid gases and hydrocarbons over the years.
Its monitoring is crucial for the safety and integrity of the company’s assets. One common approach
is the use and assessment of coupons in the field research. The molecular weight and mechanical
properties act as a predictive approach to polymer degradation. It did not explain the process of
damage, neither when it began nor how it continued.
5. Future Suggestions
The usage of coupons is more of a conventional approach; online monitoring is required if we are
to find the premature failure in the polymer liner in oil and gas pipelines. As far as future prospects
are concerned, the dielectric property is of the utmost importance. It may be used as an alternative
means of monitoring the damage mechanism. For this purpose, experimental work will be required,
impedance can be determined using different methods, and this value can be correlated with the
dielectric property. It may be useful for quantitative measures to identify the degradation stages in
the material after permeation damage. The outcomes of the dielectric property contribute to a more
comprehensive and systematic post permeation monitoring approach. In this way, we can establish
some acceptance requirements for the remaining polymer life.
Author Contributions: Conceptualization, H.U.K. and M.C.I.; methodology, H.U.K.; validation, M.C.I., N.N.
and H.U.K.; formal analysis, H.U.K.; investigation H.U.K. and M.C.I.; resources, M.C.I. and N.N.; data curation,
H.U.K.; writing—original draft preparation, H.U.K.; writing—review and editing, M.C.I. and N.N.; visualization,
H.U.K.; supervision, M.C.I. and N.N.; project administration, M.C.I. and N.N.; funding acquisition, M.C.I. All
authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by YUTP-FRG grant (015LC0-163).
Acknowledgments: The authors acknowledge the Universiti Teknologi PETRONAS.
Conflicts of Interest: The authors declare no conflict of interest.
Polymers 2020, 12, 2307 15 of 31
Appendix A
Table A1. Failures of NMP material.
1. The author discussed the polymers applications along with design strategies
and failure mechanisms.
Oilfield Engineering with Polymers [111] Thermal aging, Permeation 2. Perfluoro ether is better than Fluor elastomers in terms of temperature 2006
flexibility and resistance to acids and alkalis.
3. Fluor elastomers are considered best for downhole applications.
1. One of the pipelines installed by Shell Canada Energy was failed after
Corrosion failure in a lined sour gas four years.
Permeation 2010
pipeline—part 1: Case history of incident [116] 2. Methanol permeates through the liner due to its high vapor pressure than
water and caused failure.
Long-term Behavior of Polyethylene PE 80 1. The simulated imperfections were introduced to predict the service life of
Pressurized Pipes, in Presence of Longitudinal Imperfection the PE-80 pipe. 2010
Simulated Imperfections [118] 2. Ductile to brittle transition occurred, and the formation of cracks was seen.
1. The PE pipe was squeezed for repair, but it produces the compressive forces
Analysis of a Failure in a Polyethylene Gas Pipe
Compressive Stress on it.
Caused by Squeeze off Resulting in an 2012
(Brittle Fracture) 2. The stress concentrates on the inner surface of the pipe wall; covalent bonds
Explosion [124]
broke down and caused the nucleation of brittle fracture.
1. The crack was initiated due to the flowing pressure in the inner protective layer.
Multilayer polymer pipes failure assessment
Creep 2. In case of low adhesion between protective and main pipe, the crack propagates 2013
based on a fracture mechanics approach [129]
through the interface and vice versa.
Failure analysis of anticorrosion plastic alloy
1. The higher resin content and a lower degree of cure decrease the Tg, which affects the
composite pipe used for oilfield gathering and Processing 2013
thermal stability and mechanical strength.
transportation [126]
1. The SCG occurred at a low-stress level below the yield point.
Influence of specimen geometry on the slow crack 2. The formation of crack followed the crazing and micro-voids.
Creep 2015
growth testing of HDPE for pipe applications [130] 3. The resistance to crack growth was studied by different geometries of PE sample using
PENT and CDNT tests.
1. PA6 was thermally aged, and the decrease in Young’s modulus found out.
Evaluation of Long-Term Behaviour of Polymers
Thermal aging 2. The hydrostatic pressure increases the weight gain by the epoxy resins in the case 2015
for Offshore Oil and Gas Applications [131]
of voids.
1. Impact and cyclic fatigue are the most common failures associated with polymers.
Crack Damage in Polymers and Composites: A 2. In Fiber-Reinforced Composites, the failure occurs in terms of debonding of the
Fatigue 2016
Review [133] fibre–matrix interface, matrix fracture, stress redistribution, fibre fracture,
and fibre pullout.
1. The fatigue requires three stages, initiation of microcrack, propagation, and rupture.
HDPE pipes failure analysis and damage 2. Almost 50–90% of mechanical failures are due to fatigue.
Fatigue 2016
modeling [134] 3. Notched specimens of HDPE tested, and their results were validated by damage
models to predict the critical life fraction.
Polymers 2020, 12, 2307 19 of 31
Influence of aging in the failure pressure of a 1. The GFRP pipes were aged using the temperature (80 ◦ C) and pressure (1 MPa).
Thermal aging 2016
GFRP pipe used in oil industry [135] 2. The stiffness of the material is not affected, but the UTS is reduced by aging.
“Failure of glass fiber-reinforced epoxy pipes in oil
1. Diffusion caused the matrix plasticization, and swelling also reached the
fields.” Handbook of Materials Failure Analysis Permeation
fiber-matrix interface. 2016
with Case Studies from the Oil and Gas (diffusion)
2. Tg decreased as well as mechanical properties degraded.
Industry [136]
1. The GFRP were aged in petroleum water for 1440h.
Fracture and Mechanical Characteristics
2. The presence of quartz particles in the epoxy resin allows the absorption of
Degradation of Glass Fiber-Reinforced Petroleum Chlorides 2016
liquid chlorides.
Epoxy Pipes [137]
3. The fracture occurred, followed by the fiber breaking, pull out, and matrix breaking.
1. HDPE liner failed after 24 months due to crude oil and high pressure in Lone Creek
Case Study: Engineered Polyamide 12 (PA12)
Field, Canada.
Pipeline Liner for Management of Sour Gas Permeation 2017
Corrosion at Elevated Temperatures [102] 2. PA12 was installed, and its performance checked after one year; permeation rates are
not critical.
Nonmetallics applications in oil and gas 1. A 3-inch RTP line with Polyphenylene sulfide (PPS) liner operating at 8 bar and 95 ◦ C
production (pipes, liners, rehabilitations), CO2 cracking, contains the produced fluid with high CO2 (47mol %), 5ppm H2 S, and 97% water cut.
2017
in Trends in Oil and Gas Corrosion Research and Thermal aging 2. It failed after two years in service due to cracking caused by the high CO2 content, high
Technologies [5] temperature, and the manufacturing anomalies acting as stress concentrators.
1. The multi-layer composite pipe has the ultimate fundamental properties to deliver fuel
Poor handling,
Study of Multilayered Composite Pipe subjected and natural gas.
Stress 2018
with Metal Interlayer [139] 2. The internal layer will undergo brittle fracture; polymers like PE, PP, etc. can provide
concentrators
resistance against the internal environment.
1. The PA-11 was aged in water and organic acids; the molecular weight degradation
Polymer crystallinity and the ductile to brittle Permeation increases the crystallinity.
2018
transition [140] (Immersion) 2. Ductility decreased due to chemi-crystallization.
3. The heat of fusion value determined the transition from ductile to brittle.
Polymers 2020, 12, 2307 20 of 31
1. The failure rate of PE in gas distribution networks was given from the company in Poland is λp
Approaches for Safety Analysis of Gas Pipeline
Mechanical Damage = 0.18 km−1 a−1 .
Functionality in Terms of Failure Occurrence: A 2018
(outside) 2. The percentage of failure (95.28%) is mainly supported by mechanical damage, including human
Case Study [141]
activity, out of date plans, and building of other infrastructures.
Innovative Field Trial Results of Flangleess
1. ADNOC installed a 3-inch grooved HDPE liner in one of their onshore oil fields.
Grooved HDPE Liner Application in a Super
Permeation 2. After five years of service, testing was carried out, and the reduction in density and permeation 2018
Gigantic Field for Oil Flow Line Internal
Corrosion Management [142] of hydrocarbons was seen by GC-MS analysis
Failure Analysis of Buried Polyethylene Pipe 1. The PE pipes used for urban gas transportation are more prone to landslide, settlement,
Subjected to Combined Loading of Non-uniform Outside damage and traffic load. 2018
Settlement and Landslide Based on FEM [143] 2. The damage caused by a landslide is more prominent than settlement.
Sustainable and safe in exploitation of gas 1. The PE pipe used for the transportation of natural gas were frequently failed due to human error.
networks. Part1. Stress factors of plastic Human error 2. These include the defective installation design, poor handling, and failure to comply with 2018
pipelines [144] technical regulations.
Thermal-oxidative aging performance and life 1. The presence of carbonyl and hydroxyl groups on the surface-displayed thermal oxidation.
prediction of polyethylene pipe under cyclic and Thermal aging 2. The internal cyclic pressure broke the molecular chains rapidly and promoted degradation. 2019
constant internal pressure [145] 3. The life of PE100 facing cyclic stress is 27.96% shorter than constant stress.
Analysis of cracks in polyvinylidene fluoride lined 1. The PVDF liner was used for transporting oil and gas at 90 bar and 37 ◦ C in the presence of
reinforced thermoplastic pipe used in acidic gas Weld cracks acidic gases. 2019
fields [146] 2. The liner failed after six months due to weld lines formed after improper processing.
Creep behavior of in-service flexible flowline 1. The samples were taken from 3 different layers of PA11 flexible pipe after three years.
Permeation 2020
polyamide 11 [81] 2. The chain scission occurred, which in turn reduces the CIV value and elastic modulus.
Development of Carbon Fiber Based Structural
1. Leakage is mainly observed in internally pressurized pipes.
Health Monitoring System for Glass Internal Pressure
2. The matrix cracking occurred due to an increase in static or cyclic loading. 2020
Fiber-Reinforced Polymer Composite (Creep & Fatigue)
Conduits [147] 3. Due to the low strength of the matrix, delamination occurred.
1. The impact resistance of the PA pipe is better than HDPE and MDPE pipe.
Damage evaluation and protection method of
resin pipe for gas conduit subjected to impact Third-party damage 2. The MDPE pipe with protective sheets, including reinforced fiber and non-woven fiber provide 2020
load [148] better static and impact resistance than the HDPE pipe. In 2015 the US Department of Energy
provided that the gas distribution sector contained mostly plastic pipes to cater corrosion.
Polymers 2020, 12, 2307 21 of 31
Environment
Materials Parameters Permeation Outcomes Ref
(Gases or Liquids)
T: ambient
CO2, CH4 , Aromatic 1. MDPE swells up to 15% in the presence of hydrocarbons.
MDPE P: 100 psi [149]
hydrocarbon 2. CO2 has greater permeation in MDPE than CH4 .
Thick: 10 mm
1. Pe and S coefficients increase due to an increase in thickness.
T:40,60,81 ◦ C
2. Pe and D coefficients increase as pressure increases.
HDPE CO2 , CH4 P: 4 MPa [150]
Thick: 2 mm 3. In the case of CO2 , the Pe and D coefficients value increases as compared to S by
increasing temperature.
T:50 ◦ C
PE80,
33% H2 S, 10% CO2 , P: 40 & 80 bar 1. Permeation of acidic gases creates corrosive conditions in the annulus.
PE-X, [151]
70% CH4 Thick: 5 mm 2. The corrosion product layers were greater in the case of 80 bar.
PE-DB (Al-foil)
Duration: 3 months
T: 60 ◦ C 1. The CO2 molecules diffusivity is greater than CH4 .
CO2 , CH4 ,
PE-80 P: 40 bars 2. In the case of a mixture of gases, no particular gas-gas and gas-polymer interaction [152]
CO2 /CH4 , H2 /CH4
Thickness: 1–3 mm were observed.
T: 20,50,80 ◦ C
1. No effect on the mechanical properties observed after the aging process.
PE100 H2 , CH4 P: 5 & 20 bars
2. PE100 is more permeable to H2 than PA11. [97]
PA11 Thick: 1 mm
Duration: 13 months 3. Pe coefficient is unaffected at 20 ◦ C under pure H2 .
CO2 , H2 S, CH4 ,
PA (TP30) T: 140 ◦ C 1. Water has a more prominent effect as compared to gases. [153]
Liquid (H2 O)
T: 100 ◦ C
1. SOUR JIP investigated the performance of PVDF at MERL ltd.
PVDF H2 S P: 60–70 bars [42]
Duration:339 days 2. No effect was observed on the weight and mechanical properties of PVDF liner.
T: 20,50,80 ◦ C
PE100, 1. The degree of crystallinity is higher for HDPE than for others.
P: 5 & 20 bars
PA11, H2 , CH4 2. Permeation rates for H2 are higher despite the temperature, pressure, and the mixture [154]
Thick: 1 mm
PAHM of gases.
Duration: 1 year
Polymers 2020, 12, 2307 22 of 31
Environment (Gases or
Materials Parameters Permeation Outcomes Ref
Liquids)
T: ambient
HDPE, 1. No significant change was observed in Tg and tensile strength.
H2 P:100 MPa [155]
PTFE 2. HDPE has a lower permeability than PTFE due to higher crystallinity.
Duration: one week
T: 45 ◦ C 1. The Pe coefficients of methane and light hydrocarbons in HDPE is higher as compared
PA12, 12.5% H2S, 1.3% CO2 ,
P: 290 psi to PA12. [102]
HDPE crude oil
Thick: 6.7 mm 2. Tensile modulus decreased while elongation at break increased.
T: 80 & 100 ◦ C
1. The Pe and D coefficients increase with temperature in the presence of CO2 .
PPS, PEEK CO2 , H2 S P: 400 bars [156]
Thick: 2.3 mm 2. The solubility of H2 S is not prominent due to low partial pressure (2.25 bar).
T: 25 ◦ C
1. Ammonia has a greater affinity for PFA.
TFE (PFA) HCl, NH4 Thick: 0.25 mm, round sample with [157]
4.6 cm dia 2. Ammonia has higher Pe and D coefficients as compared to HCl.
PA12 (PVDF T: 110 ◦ C 1. Molar mass was reduced, and the inner surface of the layer dissolved due to aging.
Ethanol [159]
outer layer) Duration: 2400 h 2. The pipe became stiffer due to the loss of plasticizer.
T: 20–40 ◦ C 1. In biofuel, tensile strength first decreased then increased due to thickness variation. Its
HDPE with PA Biofuels (E85, Biodiesel,
Thick: 1.4–1.6 mm vice versa happened in biodiesel. [160]
barrier B10)
Duration: 5 years. 2. No noticeable change was observed in the FTIR spectra.
E10(CE10A),
HDPE, 1. 10% volume change for PVDF and 16% for HDPE was observed.
55% butanol (CB55A) Duration: 16 weeks. [161]
PVDF 2. The samples show a reduction in % elongation.
10% Ethanol
1. Mass and volume change was observed.
E30 (ethanol-gasoline) T: 45 ◦ C
HDPE 2. Yield strength increases because of the absorbed fuel act as a plasticizer. [162]
B30 (biodiesel) Duration: 1608 h
3. Impact strength improves significantly due to the appearance of ductility after soaking.
PE100 Brine, NORSOK M-710 (70% heptane, 1. Elastic modulus decreased, and its value is prominent at 80 ◦ C.
T: 23,50,80 ◦ C [164]
PE-RT 20% cyclo-hexanes & 10% toluene) 2. Oil saturation gives swelling, which affects the mechanical properties.
T: 150 ◦ C 1. The diffusion and solubility coefficients have a linear relationship with temperature.
PVDF CO2 , CH4 [165]
P: 300 bars 2. Above 100 ◦ C, the permeation of CO2 increased.
1. The composite film provides impermeable performance due to the presence of the Al
LDPE, T: Ambient
Gases: CO2 , CH4 , H2 O continuous layer. [88]
PA11 P: 24 bars
2. The mass gain due to corrosion products was higher in LDPE and nylon.
T: 60 ◦ C 1. The gas solubility got decreased at high pressures due to the hydrostatic effect.
PE-80 Gases: CO2 , CH4 , H2 S P: 2k bars 2. The volume of the amorphous phase decreased down to 6% at 2k bars due to less free [166]
Thick: 1–4 mm volume available.
1. The anti-H2 S layer stopped the permeation due to the presence of PEZnO.
T:80 ◦ C
PA11 H2 S 2. This zinc oxide has higher reactivity with H2 S, proved by a full-scale flowline [167]
P: 200 bars
qualification test.
PA11 CO2 , T: 80,100,120 ◦ C 1. The CIV value of PA11 was lower than PA12 after aging.
[168]
PA12 H2 O, Crude oil P: 20 bars 2. PA12 has good % elongation.
1. The abrasive wear resistance of HDPE was 3.2 times better than CS.
HDPE CO2 , water, and sand [169]
2. After the 12 months field trial, no swelling or softening in HDPE was observed.
1. Toluene has a more aggressive impact on HDPE than methanol. It took around one week
HDPE Methanol, 1-butanol [170]
to reach equilibrium as compared to 1-butanol.
1. The volume fractions were almost the same for both excluding toluene.
HDPE, crude oil, toluene, cyclohexane,
2. The value of young’s modulus and the yield stress affected the swollen samples due to [171]
XLPE and n-heptane
the plasticization of the amorphous components
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